HERBICIDAL COMPOSITIONS

HERBICIDES

English Abstract

IN THE UNITED STATES PATENT OFFICE
HERBICIDE COMPOSITIONS
Abstract of the Disclosure
Herbicidal active sulfoxide and
sulfone compounds are described herein. The compounds
have the following generic formula:
<IMG>
wherein n is 1 or 2; R is selected from the group con-
sisting of lower alkyl, haloalkyl, alkoxyalkenyl and
alkenyl; R1 and R2 can be the same or different and
can be selected from the group consisting of hydrogen,
lower alkyl, cycloalkyl, alkenyl and alkynyl provided
that when R1 is hydrogen R2 is other than hydrogen.

Claims

WHAT IS CLAIMED IS:
1. A compound represented by the following generic
formula:
<IMG>
wherein n is 1 or 2; R is selected from the group consisting of
lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; R1 and R2 can
be the same or different and can be selected from the group con-
sisting of lower alkyl, cycloalkyl, alkylcycloalkyl, alkenyl and
alkynyl.
2. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
3. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is i-C4H9, R2 is i-C4H9 and n is 2.
4. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 2.
5. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is i-C4H9, R2 is i-C4H9 and n is 1.
6. The compound as set forth in Claim 1 wherein R is
n-C3H7, R1 is n-C4H9, R2 is -C2H5 and n is 1.
7. The compound as set forth in Claim 1 wherein R is
n-C3H7, R1 is n-C4H9, R2 is -C2H5 and n is 2.
8. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is <IMG> , R2 is -C2H5 and n is 2.
17

9. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is <IMG> , R2 is -C2H5 and n is 1.
10. The compound as set forth in Claim 1 wherein R is
n-C3H7, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
11. The compound as set forth in Claim 1 wherein R is
n-C3H7, R1 is n-C3H7, R2 is n-C3H7 and n is 2.
12. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is -CH2-CH=CH2, R2 is -CH2-CH2-CH3 and n is 1.
13. The compound as set forth in Claim 1 wherein R is
n-C3H7, R1 is -C2H5, R2 is -C2H5 and n is 1.
14. The compound as set forth in Claim 1 wherein R is
n-C3H7, R1 is -C2H5, R2 is <IMG> and n is 1.
15. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is -CH2-CH=CH2, R2 is -CH2-CH=CH2 and n is 1.
16. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is -CH3, R2 is -CH(CH3)-C=CH and n is 1.
17. The compound as set forth in Claim 1 wherein R is
-CH2-CH=CH2, R1 is -CH2-CH=CH2, R2 is -CH2-CH=CH2 and n is 2.
18. The compound as set forth in Claim 1 wherein R is
n-C3H6-C1, R1 is -C2H5, R2 is -C2H5 and n is 1.
19. The compound as set forth in Claim 1 wherein R is
n-C3H6-C1, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
18

20. The compound as set forth in Claim 1 wherein R is
-CH=CHO-C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
21. The compound as set forth in Claim 1 wherein R is
n-C3H6-C1, R1 is -CH3, R2 is <IMG> and n is 1.
22. The compound as set forth in Claim 1 wherein R is
-n-C3H6-C1, R1 is -C2H5, R2 is C2H5 and n is 1.
23. The compound as set forth in Claim 1 wherein R is
-n-C3H6-C1, R1 is -n-C3H7, R2 is -n-C3H7 and n is 1.
24. The compound as set forth in Claim 1 wherein R is
-n-C3H6-C1, R1 is -C2H5, R2 is -n-C4H9 and n is 1.
25. The compound as set forth in Claim 1 wherein R is
-n-C3H6-C1, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
26. The compound as set forth in Claim 1 wherein R is
-n-C3H6-C1, R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
27. The compound as set forth in Claim 1 wherein R is
-n-C3H6-C1, R1 is -i-C4H9, R2 is -i-C4H9 and n is 1.
28. The compound as set forth in Claim 1 wherein R is
-n-C3H6-C1, R1 is -C2H5, R2 is <IMG> and n is 1.
29. The compound as set forth in Claim 1 wherein R is
-n-C4H6. R1 is -CH3, R2 is -CH2<IMG> and n is 1.
19

30. The compound as set forth in Claim 1 wherein R is
-i-C4H9, R1 is -CH3, R2 is <IMG> and n is 1.
31. The compound as set forth in Claim 1 wherein R is
-sec-C4H9, R1 is -CH3, R2 is <IMG> and n is 1.
32. The compound as set forth in Claim 1 wherein R is
-n-C3H6-C1, R1 is -CH3, R2 is <IMG> and n is 1.
33. The compound as set forth in Claim 1 wherein R is
-CH2-CHC1-CH2C1, R1 is -CH3, R2 is <IMG> and n is 1.
34. The compound as set forth in Claim 1 wherein R is
-CH(CH2C1)2, R1 is -CH3, R2 is <IMG> and n is 1.
35. The compound as set forth in Claim 1 wherein R is
-n-C3H7, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
36. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
37. The compound as set forth in Claim 1 wherein R is
-n-C4H9, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
38. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is -n-C3H7, R2 is -i-C4H9 and n is 1.

39. The compound as set forth in Claim 1 wherein R is
-i-C3H7, R1 is -n-C3H7, R2 is -i-C4H9 and n is 1.
40. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is -C2H5, R2 is -i-C4H9 and n is 1.
41. The compound as set forth in Claim 1 wherein R is
-n-C3H7, R1 is -i-C4H9, R2 is -C2H5 and n is 1.
42. The compound as set forth in Claim 1 wherein R is
-C2H5, R1 is -i-C4H9, R2 is -i-C3H7 and n is 1.
43. The compound as set forth in Claim 1 wherein R is
-n-C3H7, R1 is -i-C3H7, R2 is -n-C4H9 and n is 1.
44. The compound as set forth in Claim 1 wherein R is
-CH3, R1 is -C2H5, R2 is <IMG> and n is 1.
45. The compound as set forth in Claim 1 wherein R is
-i-C3H7, R1 is -C2H5, R2 is <IMG> and n is 1.
46. The compound as set forth in Claim 1 wherein R is
-n-C4H9, R1 is -C2N5, R2 is <IMG> and n is 1.
47. The compound as set forth in Claim 1 wherein R is
-i-C4H9, R1 is -C2H5, R2 is <IMG> and n is 1.
21

48. The compound as set forth in Claim 1 wherein R is
-n-C3H6-C1, R1 is -C2H5, R2 is <IMG> and n is 1.
49. The compound as set forth in Claim 1 wherein R is
-CH2-CHC1-CH2C1, R1 is -C2H5, R2 is <IMG> and n is 1.
50. The compound as set forth in Claim 1 wherein R is
-i-C3H7, R1 is -n-C3H7, R2 is <IMG> and n is 1.
51. The compound as set forth in Claim 1 wherein R is
-n-C4H9, R1 is -n-C3H7, R2 is <IMG> and n is 1.
52. The compound as set forth in Claim 1 wherein R is
.
-i-C4H9, R1 is -n-C3H7, R2 is <IMG> and n is 1.
53. The compound as set forth in Claim 1 wherein R is
-sec-C4H9, R1 is -n-C3H7, R2 is <IMG> and n is 1.
54. The compound as set forth in Claim 1 wherein R is
-n-C3H6-C1, R1 is -n-C3H7, R2 is <IMG> and n is 1.
55. The compound as set forth in Claim 1 wherein R is
-CH2-CHC1-CH2C1, R1 is -n-C3H7, R2 is <IMG> and n is 1.
22

56. The compound as set forth in Claim 1 wherein R is
-n-C3H7, R1 is -C2H5, R2 is <IMG> and n is 1.
57. The method of controlling undesirable vegetation
comprising applying to the locus where control is desired an
herbicidally effective amount of a compound represented by the
following generic formula:
<IMG> .
wherein n is 1 or 2; R is selected from the group consisting of
lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; R1 and R2 can
be the same or different and can be selected from the group con-
sisting of lower alkyl, cycloalkyl, alkylcycloalkyl, alkenyl and
alkynyl.
58. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
59. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is i-C4H9, R2 is i-C4H9 and n is 2.
60. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 2.
61. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is i-C4H9, R2 is i-C4H9 and n is 1.
62. The method as set forth in Claim 57 wherein R is
n-C3H7, R1 is n-C4H9, R2 is -C2H5 and n is 1.
63. The method as set forth in Claim 57 wherein R is
n-C3H7, R1 is n-C4H9, R2 is -C2H5 and n is 2.
64. The method as set forth in Claim 57 wherein R is
-C2H5, Rl is <IMG>, R2 is -C2H5 and n is 2.
23

65. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is <IMG> , R2 is -C2H5 and n is 1.
66. The method as set forth in Claim 57 wherein R is
n-C3H7, R1 is n-C3H7, R2,is n-C3H7 and n is 1.
67. The method as set forth in Claim 57 wherein R is
n-C3H7, R1 is n-C3H7, R2 is n-C3H7 and n is 2.
68. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is -CH2-CH-CH2, R2 is -CH2-CH2-CH3 and n is 1.
69. The method as set forth in Claim 57 wherein R is
n-C3H7, R1 is -C2H5, R2 is -C2H5 and n is 1.
70. The method as set forth in Claim 57 wherein R is
n-C3H7, R1 is -C2H5, R2 is <IMG> and n is 1.
71. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is -CH2-CH-CH2, R2 is -CH2-CH-CH2 and n is 1.
72. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is -CH3, R2 is -CH(CH3)-C?CH and n is 1.
73. The method as set forth in Claim 57 wherein R is
-CH2-CH=CH2, R1 is -CH2-CH=CH2, R2 is -CH2-CH=CH2 and n is 2.
74. The method as set forth in Claim 57 wherein R is
n-C3H6, R1 is -C2H5, R2 is -C2H5 and n is 1.
75. The method as set forth in Claim 57 wherein R is
n-C3H6, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
24

76. The method as set forth in Claim 57 wherein R is
-CH=CHO-C2H5, R1 is n-C3H7, R2 is n-C3H7 and n is 1.
77. The method as set forth in Claim 57 wherein R is
n-C3H6-C1, R1 is -CH3, R2 is <IMG> and n is 1.
78. The method as set forth in Claim 57 wherein R is
-n-C3H6-C1, R1 is -C2H5, R2 is C2H5 and n is 1.
79. The method as set forth in Claim 57 wherein R is
-n-C3H6-C1, R1 is -n-C3H7, R2 is -n-C3H7 and n is 1.
80. The method as set forth in Claim 57 wherein R is
-n-C3H6-C1, R1 is -C2H5, R2 is -n-C4H9 and n is 1.
81. The method as set forth in Claim 57 wherein R is
-n-C3H6-C1, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
82. The method as set forth in Claim 57 wherein R is
-n-C3H6-C1, R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
83. The method as set forth in Claim 57 wherein R is
-n-C3H6-C1, R1 is -i-C4H9, R2 is -i-C4H9 and n is 1.
84. The method as set forth in Claim 57 wherein R is
-n-C3H6-C1, R1 is -C2H5, R2 is <IMG> and n is 1.
85. The method as set forth in Claim 57 wherein R is
-n-C4H6, R1 is -CH3, R2 is <IMG> and n is 1.

86. The method as set forth in Claim 57 wherein R is
-i-C4H9, R1 is -CH3, R2 is <IMG> and n is 1.
87. The method as set forth in Claim 57 wherein R is
-sec-C4H9, R1 is -CH3, R2 is <IMG> and n is 1.
88. The method as set forth in Claim 57 wherein R is
-n-C3H6-C1, R1 is -CH3, R2 is <IMG> and n is 1.
89. The method as set forth in Claim 57 wherein R is
-CH2-CHC1-CH2C1, R1 is -CH3, R2 is <IMG> and n is 1.
90. The method as set forth in Claim 57 wherein R is
-CH(CH2C1)2, R1 is -CH3, R2 is <IMG> and n is 1.
91. The method as set forth in Claim 57 wherein R is
-n-C3H7, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
92. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is -n-C4H9, R2 is -n-C4H9 and n is 1.
93. The method as set forth in Claim 57 wherein R is
-n-C4H9, R1 is -i-C3H7, R2 is -i-C3H7 and n is 1.
94. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is -n-C3H7, R2 is -i-C4H9 and n is 1.
26

95. The method as set forth in Claim 57 wherein R is
-i-C3H7, R1 is -n-C3H7, R2 is -i-C4H9 and n is 1.
96. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is -C2H5, R2 is -i-C4H9 and n is 1.
97. The method as set forth in Claim 57 wherein R is
-n-C3H7, R1 is -i-C4H9. R2 is -C2H5 and n is 1.
98. The method as set forth in Claim 57 wherein R is
-C2H5, R1 is -i-C4H9, R2 is -i-C3H7 and n is 1.
99. The method as set forth in Claim 57 wherein R is
-n-C3H7, R1 is -i-C3H7, R2 is -n-C4H9 and n is 1.
100. The method as set forth in Claim 57 wherein R is
-CH3, R1 is -C2H5, R2 is <IMG> and n is 1.
101. The method as set forth in Claim 57 wherein R is
-i-C3H7, R1 is -C2H5, R2 is <IMG> and n is 1.
102. The method as set forth in Claim 57 wherein R is
-n-C4H9, R1 is -C2H5, R2 is <IMG> and n is 1.
103. The method as set forth in Claim 57 wherein R is
-i-C4H9, R1 is -C2H5, R2 is <IMG> and n is 1.
27

104. The method as set forth in Claim 57 wherein R is
-n-C3H6-C1, R1 is -C2H5, R2 is <IMG> and n is 1.
105. The method as set forth in Claim 57 wherein R is
-CH2-CHC1-CH2C1, R1 is -C2H5, R2 is <IMG> and n is 1.
106. The method as set forth in Claim 57 wherein R is
-i-C3H7, R1 is -n-C3H7, R2 is <IMG> and n is 1.
107. The method as set forth in Claim 57 wherein R is
-n-C4H9, R1 is -n-C3H7, R2 is <IMG> and n is 1.
108 . The method as set forth in Claim 57 wherein R is
-i-C4H9, R1 is -n-C3H7, R2 is <IMG> and n is 1.
109. The method as set forth in Claim 57 wherein R is
-sec-C4H9, R1 is -n-C3H7, R2 is <IMG> and n is 1.
110. The method as set forth in Claim 57 wherein R is
-n-C3H6-C1, R1 is -n-C3H7, R2 is <IMG> and n is 1.
111. The method as set forth in Claim 57 wherein R is
-CH2-CHC1-CH2C1, R1 is -n-C3H7, R2 is <IMG> and n is 1.
28

112. The method as set forth in Claim 57 wherein R is
-n-C3H7, R1 is -C2H5, R2 is <IMG> and n is 1.
113. A process for manufacturing pesticidal active com-
pounds corresponding to the following formula:
<IMG>
wherein n is 1 or 2; R is selected from the group consisting of
lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; R1 and R2 can
be the same or different and can be selected from the group con-
sisting of lower alkyl, cycloalkyl, alkylcycloalkyl, alkenyl and
alkynyl; comprising the steps of:
a. combining an oxidizing agent and a thio-
carbamate compound in a solvent system; said thio-
carbamate having the following formula:
<IMG>
wherein R, R1 and R2 have been defined above;
b. maintaining the temperature between -15°C.
and 60°C.;
c. said oxidizing agent being present in an
amount of at least one stoichiometric equiva-
lent and not more than two stoichiometric
equivalents.
114. The process as set forth in Claim 113 wherein said
oxidizing agent is selected from peracetic acid and m-chloro-
peroxybenzoic acid.
29

115 Compounds of the class of carbamoyl sulphoxides
having the general formula:
<IMG>
wherein R is selected from:
- alkyl containing 1 to 4 carbon atoms;and
- haloalkyl containing l to 4 carbon atoms;
and wherein R1 and R2 can be the same or different and can be
selected from:
- alkyl containing 1 to 4 carbon atoms; and
- cycloalkyl containing 4 to 7 carbon atoms.
116 The compound having the formula:
<IMG> .
117 The compound having the formula:
<IMG> .

118 The compound having the formula:
<IMG> .
119 The compound having the formula:
<IMG> .
120 The compound having the formula:
<IMG> .
121 A process for manufacturing a compound having the
general formula:
<IMG>
31

wherein R is selected from:
- alkyl containing 1 to 4 carbon atoms; and
- haloalkyl containing 1 to 4 carbon atoms;
and wherein R1 and R2 can be the same or different and can be
selected from:
- alkyl containing 1 to 4 carbon atoms; and
- cycloalkyl containing 4 to 7 carbon atoms.
comprising the steps of:
(a) reacting an oxidizing agent selected from:
(i) peracetic acid; and
(ii) m-chloroperoxybenzoic acid and a
thiocarbamate, said thiocarbamate hav-
ing the general formula:
<IMG>
wherein R, R1 and R2 have been previously defined;
(b) said reaction being carried out at a temperature
between -15°C and 50°C; and
(c) said oxidizing agent being present in an amount of
one molar equivalent.
122 A method of controlling undesirable vegetation com-
prising applying to the locus where control is desired an
effective amount of a compound represented by the general
formula:
<IMG>
32

wherein R is selected from:
- alkyl containing 1 to 4 carbon atoms; and
- haloalkyl containing 1 to 4 carbon atoms;
and wherein R1 and R2 can be the same or different and can be
selected from:
- alkyl containing 1 to 4 carbon atoms; and
- cycloalkyl containing 4 to 7 carbon atoms.
123 The method as set forth in claim C21 wherein R is
-C2H5, R1 is n-C3H7 and R2 is n-C3H7.
124 The method as set forth in claim C21 wherein R is
n-C3H7, R1 is n-C3H7 and R2 is n-C3H7.
125 The method as set forth in claim C21 wherein R is
-C2H5, R1 is i-C4H9 and R2 is i-C4H9.
126 The method as set forth in claim C21 wherein R is
n-C3H7, R1 is n-C4H9 and R2 is -C2H5.
127 The method as set forth in claim C21 wherein R is
n-C3H7, R1 is -C2H5 and R2 is <IMG>.
-33-

Description

1:~551ZS
Description of the Invention
This invention is directed to a novel group of compounds
which may be generally described as sulfoxide and sulfone deriva-
tives of thiocarbamates which are highly active herbicides.
The compounds of the present invention are represented by the
generic formula:
R-S(O)n-~-N
wherein n can be 1 or 2; R can be selected from the group consis-
ting of lower alkyl, haloalkyl, alkoxyalkenyl and alkenyl; ~1
and R2 can be the same~or different and can be selected from
the group consisting of lower alkyl, cycloalkyl having 3-8 carbon
atoms, alkylcycloalkyl, alkenyl and alkynyl.
.
The above-noted compounds can be prepared by reacting
an oxidizing agent such as peracetic acid or m-chloroperoxy-
benzoic acid with a thiocarbamate compound corresponding to the
following formula:
R-S-C-N
R2
whe~ein R, Rl and R2 have been defined above. The reaction is
carried out in the presence of an inert solvent such as chloro-
form, methylene chloride, benzene, and toluene, and at a
temperature of from about -25C. to about 60C. The amount of
oxidizing agent used must be at least one molar equivalent to form the
~ - 2 -

~5~5
sulfoxide derivative and at least two molar equivalents to form
the sulfone derivatives. The reaction is completed when no
oxidizing agent is left within the reaction mass.
The thiocarbamate compounds are known herbicides and
their method of synthesis is known; see U.S. Patents 2,913,327,
2,983,747, 3,133,947, 3,175,897 and 3,185,720 for example. How-
ever, the use of these thiocarbàmates as reactive intermediates
to form other compounds that have pesticidal activity is
unexpected.
In order to illustrate the merits of the present inven-
tion, the following examples are provided:
.xample 1
~ R n-C3H7
C2~5-S-C N
n C3 7
A mixture was formed which contained 12.2 g. (0.06 mole)
of m-chloroperoxybenzoic acid in 200 cc. of chloroform. This
solution was then cooled in an ice bath to 3C. Then, 9.5 g.
(0.05 mole) of S-ethyl dipropylthiocarbamate was rapidly added
and the temperature rose rapidly to 35C. and then decreased.
The flask containing the reaction mixture was placed under re-
frigeration for about an hour wherein white solid crystals were
observed. The solution was kept under refrigeration for 24 hours
and then was filtered while in the cold condition. It was then
washed with chloroform and then was dried. The co~bined filtrate
was washed with 3 portions of 100 cc. of 5% sodium carbonate
solution, 1 portion of 100 cc. of water, dried over magnesium
sulfate and concentrated on a rotary evaporator under water
pump vacuum, to yield 10.1 g. of product, n30 _ 1.4834.
- 3 -

l~SS~!l2S
Example 2
O O
C4E~g
C H -S-C-N
2 5 11 \i-C4Hg
A solution was formed containing 1~.2 g. of m-chloro-
peroxybenzoic acid in 200 cc. of methylene chloride. There-
after, 10.9 g. (0.05 mole) of S-ethyl diisobutylthiocarbamate
was added rapidly when the temperature of the solution was 18C.
The soIution rose rapidly to a temperature of 30C., wherein the
reaction mass was placed in an ice bath to reduce the tempera-
ture. After a period of 3 hours the cold mixture was filtered
and the cake was washed with 2 portions of 25 cc. of methylene
chloride. The combined filtrate was washed with 4 portions of
100 cc. of 5% solution bf sodium carbonate, then 2 portions of
100 cc. of water, dried over magnesium sulfate and concentrated
in a rotary evaporator under water pump vacuum to yield 11.0 g.
of product, nD ~ 1.4718.
Example 3
¦1 ~1 ~C2EI5
C2H5-~ -C-N~3
~, .
A solution was formed in a reaction vessel which con-
tained 22.3 g. (0.11 mole) of m-chloroperoxybenzoic acid in
300 cc. of methylene chloride. `Then, 10.8 g. (0.05 mole) of
S-ethyl cyclohexylethylthiocarbamate was added rapidly when the
temperature was 35C. The temperature rose to 41C., wherein
the temperature began to decrease and additional heat was applied
to maintain the temperature of 41C. The cold mixture was
filtered and the cake was washed with 2 portions of 25 cc. of methylene

~1~5~S
chloride. The com~ined filtr~te w~s washed with 4 por~ions of
100 cc. of 5/O sodlum carbonate solution and then 2 portions of
100 cc, o water, dried over magnesium sulfate and concentrated
in a rotary evaporator, irst under water pump vacuum and finally
under high vacuum to produce 11.9 g. of product, n30 _ 1.4911.
Example 4
C2H5-RS_~_N~ 2H5
Y~
A solution was formed containing 11.2 g. (0,055 mole)
of m-chloroperoxybenzoic acid in 200 cc. of methylene chloride.
Then, 10,8 g. (0.05 mole) of S-ethyl cyclohexylethylthiocarbamate
was added rapidly when the temperature was at -15,5C. The temper-
ature was allowed to rise to -14.5C. and maintained for 2 hours.
Thereafter, the temperature was allowed to reach 19.5C. The mix-
ture was filtered and the cake was washed with 2 portions of 25 cc.
methylene chloride and dried in the oven. The combined filtrate
wàs washed with 4 portions of 100 cc. of 5% solution of sodium
car~onate and 2 portions of 100 cc, of water, dried over m~gn~sium
sulfate and concen~rated in a rotary evapora~or, first under water
pump vacuum and finally under high vacuum to yield 10,4 g. of pro-
duct, n30 _ 1 5120.
Example 5
~ R ,Cl~2-cl~=cH2
C2H5 ~n-C3H7
A solution was formed containing 10.7 g. of m-chloro-
peroxybenzoic acid in 200 cc. of methylene chloride, The solution

1~55~S
was then placed in a dry ice bath to maint~in a temper~ture of
-16C. Thereafter, 9.4 g. (0.05 mole) of S-ethyl allylpropyl-
thLocarbamate was added rapidly and the temperature rose to -14.5C.
The reaction was allowed to carry out for 2 hours. During the
. reaction the te~perature was allowed to go to 15.5C. and there-
after was taken back do~n to 1C. The mixture was filtered and
.
the cake was washed with 2 portions of 25 cc. methylene chloride.
` The combined filtrate was washed with 4 portions of 100 cc. of 5~/
. solution of sodium carbonate and 2 portions of 100 cc. of water,
~10 dried over magnesium sulfate and concentrated in a rotary evapora-
`~ tor, first under water pump vacuum and finally under high vacuum
to yield 9.0 g. of product, n30 _ 1.5015.
ExamPle 6
' O O
C2H5~ _N ~CH2 CH=CH2
-CH=CH2
~ ~,
A solution was fonmed containing 10.7 g. (0.525 mole)
; of m-chloroperoxybenzoic acid in 200 cc. of methylene chloride in
1~5 a reaction vessel. The solution was cooled to -16.5C., wherein
. .
9.3 g. (0.05 mole) of S-ethyl diallylthiocarbamate was added
rapidly. Then, the solution rose to -15C. The reaction was
allowed to be carried out for 105 hours. At the end of this time
~` the reaction was allowed to reach 18.5C. The cold mixture was
filtered and the cake washed with 2 portions of 25 cc. of methylene
chloride. The combined filtrate was washed with 4 portions of
lO0 cc. of 5% sodium carbonate solution and 2 portions of 100 cc.
of water, dried over magnesium sulfate and concentrated in a rota-~
evaporator to yield 8.8 g. of product, n30 _ 1.5144.
- - 6 -

~55~5
Example 7
O O
C 2H 5--S- C-N
CH(cH8)-c-cH
A solution was formed containing 200 cc. methylene
chloride with 10.7 g. (0.0525 mole) of m-chloroperoxybenzoic acid
dissolved therein. This solution was cooled to -15C., wherein
8.6 g. (0.05 mole) of S-ethyl methyl-~.methylpropargylthiocar-
bamate was added rapidly. At the end of 2 hours the reactionwas removed from the ice bath and allowed to reach 21.5C., where-
in the reaction was worked up in a similar manner as set forth
in the previous example to yield 6.9 g. of product, nD - 1.5147.
Example 8
O O
ClCH2-CH2-CH2-S-C-N ~ 2 5
C2H5
A solution was formed containing 200 cc. of methylene
chloride and 11.6 g. of S-3-chloropropyldiethylthiocarbamate dis-
solved therein. This solution was cooled to -17C. in dry ice
bath, wherein 10.0 g. of m-chloroperoxybenzoic acid was added
rapidly. After 2 hours the reaction was removed from the dry
ice bath and allowed to reach 18.5C. wherein the reaction was
worked-up in a similar manner as set forth in the p~evious
example to yield 11.1 g. of product, nD - 1.5107.
Other compounds were prepared in an analogous manner
starting with the appropriate starting materials as outlined
above. The following is a table of compounds representative of
those embodied by the present invention. Compound numbers have
been assigned to them and are used for identification throughout
the balance of the specification.
~ - 7 -

~1~5~5
TABLE I
Il R
Physic~l
Const~nt
Compound ~0
Number R Rl R2 - n~ or o r,
1 -C2H5 3 7 n-C3H7 1 1,4834
2 -C2H5 i~C4Hg i-C4H9 2 1 G 4718
3 2 S 3 7 n C3 7 2 1.4574
4 C2H5 i-C4Hg i-C4H9 1 1.4834
r.-C3H7 4 4 -C2H5 1 1.4847
6 n C3H7 n C4H9 -C2H5 2 1.4657
7 -C2H5 - ~ -C2H5 2 1.4911
8 C2H5 ~ -C2H5 1 1.5122
9 n-C3H7 n-C31~7 n 3 7 1 1.4842
n C31~7 n C3~7 n C3H7 2 1.4652
11 -C2H5CH2 CH CH2 -CH2-CH2-CH3 1 1.5015
12 n C3 7 -C2H5 -C2H5 1 1.4888
13 n~C3H7 -C2H5 _ ~ 1 1.5099
14 -C2H5-CH2-CH=CH2 -C~2-CH=CH2 1 1.51L4
-C2H5 -CH3 -cH(cH3)-c-~ 1 1.5147

115512
TA13l,~ I (Cont.)
Physical
Constant
Compound
Number R Rl R2 n n30 or C
16 -CH2-CH=CH2 -CH2-c~=cH2 -CH2-CH=CH2 2yello~ oil
17 n-C3H6-Cl -C2H5 -C2H5 11.5107
l& n-C3~16~Cl 3 7 n~C3H7 11.5032
19 -cH=cHo-c2Hs n~C3H7 n C3H7 11.5082
n-C3H6-Cl -CH3 - ~ l82-90C.
21 n C3 6 Cl -C2H5 -C~H5 11.5107
22 n C3 6 Cl -n-C3H7 -n-C3H7 11.5032
23 3 6 l -C2H5 -n-C4H9 11.5019
24 3 6 -i-C3H7 -i-C3H7 11.5065
n C3H6 Cl -n-C4Hg -n-C4H9 11.4986
26 C3 6 Cl -i-C4Hg -i-C4H9 11.4977
27 n C3H6 Cl C2H5 ~ 11.5250
28 -n-C4H6 -C~3 -CH2 ~ 11,5088
29 -i-C4Hg -CH3 -CH2 ~ 168.5-74,0C.
-sec-C4Hg -CH3 -CH2 ~ 11,5122

115S~L~5
TA~L!~' I (collt-.~
Physical
Const~nt
Compound 30
Number R Rl R2 n nD or C,
31 -n-C3H6-Cl -CH3 -CH2 ~ ' 1 1.5272
32 -CH2-CIICl C~2Cl C~13 -CH2 ~ 1 Pasty solid
33 -CH(CH2C1)2 -CH3 -CH2 ~ 1 1.5346
34 -n-C3H7 -i-C3H7 -i-C3H7 1 1.4901
-C2H5 -n-C4Hg -n-C4Hg 1 1,4861
36 -n-C4Hg -i-C3H7 -i-C3H7 1 1.4821
37 -C2H5 -n-C3H7 -i-C4H9 1 1.4839
38 -i-C3H7 -n-C3H7 -i-C4H9 1 1.4840
39 -C2H5 -C2H5 -i-C4H9 1 1,4829
-n-C3H7 -i-C4Hg - C 2H5 1 1.4791
41 -C2H5 -i-C4Hg -i-C3H7 1 1.4801
42 -n-C3H7 -i-C3H7 n C4H9 1 1.4828
43 -CH3 C2H5 -CH2 ~ 1 1.5130
44 -i-C3H7 -C2H5 -CH2- ~ 1 1.5052
-n-C4~9 -C2H5 -CH2 ~ 1 1.5040
- 10 -

` 1155~12S
TA13LE l ~ont. 2
Physic?.l
Conc;t ~.n~
Comp~und ~-
Number R Rl R2 n nD or C.
46 -i-C4Hg -C2~5 -CH2 ~ 1 1.5049
47 -n-C3H6-Cl -C2H5 -CH2 ~ 1 1,5168
48 -CH2-CHCl-CH2Cl -C2H5 -CU2 ~ 1 1.5288
49 -i-C3H7 -n-C3H7 -CH2 ~ 1 1.5053
-n-C4Hg -n-C3H7 -CH ~ 1 1. 50G9
51 -L-C4Hg -n-C3H7 -CH2 ~ 1 1.5035
52 -sec-C4H9 -n-C3H7 -CH2 ~ 1 1.5042
53 -n-C3H6-Cln C3H7 -CH ~ 1 1.5142
54 -CH2-CHCl-CH2Cl -n-C3H7 -CH2- ~ 1 1.52jS
-n-C3H7 -C2H5 -CH2 ~ 1 1.5068
- 11 -

5~
Herbicidal Screening Tests
~ s previously mentioned, the novel compounds herein
described are phytotoxic compounds which are useful and valuable
in controlling various plant species. Compounds of this inven-
tion are tested as herhicides in the following manner.
Pre-emergence Herbicides Screening Test
Using an analytical balance, 20 mg. of the compound to
be tested is weighed out on a piece of glassine weighing paper.
The paper and compound are placed in a 30 ml. wide-mouth bottle
and 3 ml. of acetone containing 1% Tween 20 ~ is added to dis-
solve the compound. If the material is not soluble in acetone,
another solvent such as water, alcohol or dimethylformamide (DMF)
is used instead. When DMF is used, only 0.5 ml. or less is
used to dissolve the compound and then ano~her solvent is used to
make the volume up to 3 ml. The 3 ml. of solution is sprayed
uniformly on the soil contained in a small styrofoam flat one
day after planting weed seeds in the flat of soi~ No. 152
DeVilbiss atomizer is used to apply the~spray using compressed
air at a pressure of 5 lb./sq. inch. The rate of application is
8 lb./acre and the spray volume is 143 gal./acre.
On the day preceding treatment, the styrofoam flat
which is 7 inches long, 5 inches wide and 2.75 inches deep is
filled to a depth of 2 inches with loamy sand soil. Seeds of
seven different weed species are planted in individual rows
using one species per row across the width of the flat. The seeds
are covered with soil so that they are planted at a depth of
0.5 inch. The seeds used are hairy crabgrass (Digitaria sanguinalis~,
yell~7foxtail (Setaria qlauca), watergrass (Fchinochloa crus~alli), red oat

~155~Z5
(Avena sativa), redroot pigweed (~aranthus retroflexus), Indian
mustard (Brassica 2~ncea) and curly dock (Rumex crispus). Ample
seeds are planted to give about 20 to 50 seedlings per row after
emergence depending on the size of the plants.
After treatment, the flats are placed in the greenhouse
at a temperature of 70 to 85F. and watered by sprinkling. Two
weeks after treatment, the degree of injury or control is deter-
mined by comparison with untreated check plants of the same age.
The injury rating from 0 to 100% is recorded for each species
as per cent control with 0% representing no injury and 100%
representing complete kill.
Post-emergence Herbicide Screening Test;
Seeds of six plant species, including hairy crabgrass,
watergrass, red oat, mustard, curly dock and Pinto bean
(Phaseolus vulgaris) are planted in the styrofoam flats as
described above for pre-emergence screening. The flats are placed
in the greenhouse at 70-85~. and watered daily with a sprinkler.
About lO to 14 days after planting when the primary leaves of
the bean plants are almost fully expanded,and the first trifoliate
leaves are just starting to form, the plants are sprayed. The
spray is prepared by weighing out 20 mg. of the test compound,'
dissolving it in 5 ml. of acetone containing 1% Tween,20R and
then adding 5 ml. water. The solution is sprayed on the
foliage using a No. 152 DeVilbiss atomizer at an air pressure of
5 lb./sq. inch. The spray concentration is 0.2% and the rate
is 8 lb./acre. The spray volume is 476 gal./acre.
Injury ratings are recorded 14 days after treatment.
The rating system is the same as described above for the pre-
emergence test.
~ - 13 -

~l ~5~S
The res~lts of thcse tests are st-o~m in Table II.
TABLE I I
~n_
HERBICIDAL ACTIVITY - SCREENING RESULTS
Per Cent Control-~ at 8 lb . /A
Compound
Number Pre-emergence Post-emer~ence
99.7 63
2 74 35
3 0 33
4 99 71
99 64
6 0 43
7 o 30
8 95 50
9 98 47
o 49
1 99.9 78
12 9~-7
13 loo 85
14 88 62
39 23
16
17 81 57
18 90 84
19 44 20
67 67`
21 81 57
22 go 84
23 87 70
24 92 47

~ 5
T~r,T,], II ~Con t ~ )
Compound _I'er. CCTlt Con~rol* at 8 lb./A
Number Pre-e_n_r~ence Po~s~-emerp~cnce
~ .. . _
gg 28
26 97 64
27 91 74
28 60 52
29 58 60
47 53
31 46 0
34 91 83
96 76
36 95 82
37 94 74
38 98 84
39 99 73
93 78
41 99 71
42 100 79
43 64 27
44 99 66
97 78
46 91 67
47 71 25
49 63 61
81 65
51 82 68
52 73 63
53 63 20
. 95 77
* Average for sevcn plant species in the pre-emergence test ~nd
for si~ plant species in the post-emergence test.
- 15 -

~5~5
TAnl,T' II (Cont.)
Per C~nt Control ~t 20 ]b/Q
Compound ~ . _ _ .
~umber Pre-emer~,ence Post-emer~ence
2 56 --
3 19 -
6 13 --
7 0 __
3 ~~
32 0 10
- 33 0 10
48 0 15 -
54 0 18
Average for seven plant species in the pre-emergence test and
for six plant species in the post-emergence test.
The compounds of the present invention can be used in
any convenient form. Thus, the compounds can be made into emul-
sifiable liquids, emulsifiable concentrates, liquid, wettable
powder, powders, granular or any other convenient form, and applied
to the soil to control the undesired vegetation.
The terms lower alkyl, alkenyl and alkynyl are meant
to include those compounds having straight or branched chain con-
figurations having from 1 to 6 carbon atoms, inclusive.
- 16 -